TW202138507A - Paste resin composition, high heat-conductive material, and semiconductor device - Google Patents
Paste resin composition, high heat-conductive material, and semiconductor device Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
Abstract
Description
本發明係有關一種糊狀樹脂組成物、高導熱性材料及半導體裝置。The present invention relates to a paste resin composition, a material with high thermal conductivity and a semiconductor device.
已知一種為了提高半導體裝置的散熱性而使用含有金屬粒子的熱固性樹脂組成物來製造半導體裝置之技術。藉由使熱固性樹脂組成物含有具有比樹脂大的導熱率之金屬粒子，能夠提高該硬化物的導熱性。There is known a technique for manufacturing a semiconductor device using a thermosetting resin composition containing metal particles in order to improve the heat dissipation of the semiconductor device. By making the thermosetting resin composition contain metal particles having a thermal conductivity greater than that of the resin, the thermal conductivity of the cured product can be improved.
作為適用於半導體裝置的具體例，如以下專利文獻1及2，已知一種使用含有金屬粒子之熱固型樹脂組成物來接著/接合半導體元件和基板（支持構件）之技術。As a specific example applicable to semiconductor devices, as in Patent Documents 1 and 2 below, a technique for bonding/bonding a semiconductor element and a substrate (supporting member) using a thermosetting resin composition containing metal particles is known.
在專利文獻1中揭示了含有特定結構的（甲基）丙烯酸酯化合物、自由基起始劑、銀微粒子、銀粉及溶劑之半導體接著用熱固型樹脂組成物、以及用該組成物接合了半導體元件與基材之半導體裝置。在該文獻中記載了能夠提高對於安裝後的溫度循環的連接可靠性（0011段）。Patent Document 1 discloses a thermosetting resin composition containing a (meth)acrylate compound of a specific structure, a radical initiator, silver particles, silver powder, and a solvent, and a semiconductor bonded with the composition. Device and substrate semiconductor device. This document describes that the connection reliability with respect to the temperature cycle after installation can be improved (paragraph 0011).
在專利文獻2中揭示了含有醯亞胺丙烯酸酯化合物、自由基起始劑、填料及液狀橡膠成分之糊狀樹脂組成物、以及用該組成物接合了半導體元件與基材之半導體裝置。在該文獻中記載了藉由使糊狀樹脂組成物低應力化，能夠抑制晶片裂紋或晶片翹曲的產生（0003段）。 先前技術文獻 專利文獻Patent Document 2 discloses a paste resin composition containing an imine acrylate compound, a radical initiator, a filler, and a liquid rubber component, and a semiconductor device in which a semiconductor element and a base material are bonded using the composition. This document describes that by reducing the stress of the paste-like resin composition, the occurrence of wafer cracks or wafer warpage can be suppressed (paragraph 0003). Prior art literature Patent literature
［專利文獻1］日本特開2014-74132號公報 ［專利文獻2］日本特開2000-239616號公報[Patent Document 1] JP 2014-74132 A [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-239616
[發明所欲解決之課題][The problem to be solved by the invention]
在專利文獻1～2中記載之樹脂組成物中，半導體元件與基材接合之半導體裝置有時長期不表現出良好的導電性，在長期可靠性上存在改善的餘地。 [解決課題之技術手段]Among the resin compositions described in Patent Documents 1 and 2, the semiconductor device in which the semiconductor element and the substrate are joined may not exhibit good conductivity for a long period of time, and there is room for improvement in long-term reliability. [Technical means to solve the problem]
本發明人等發現，藉由使用具備特定結構之含（甲基）丙烯醯基之化合物，半導體裝置長期表現出良好的導電性，長期可靠性優異，從而完成了本發明。The inventors of the present invention found that by using a (meth)acrylic group-containing compound having a specific structure, a semiconductor device exhibits good electrical conductivity for a long time and has excellent long-term reliability, thus completing the present invention.
本發明能夠如下所示。 依據本發明，提供一種糊狀樹脂組成物，其含有： （A）含（甲基）丙烯醯基之化合物，其具有2官能以上，直鏈或支鏈的氧伸烷基（oxyalkylene group）的重複單元數為2以上；及 （B）含金屬之粒子，其含有含銀粒子或含銅粒子。 依據本發明，提供一種將前述糊狀樹脂組成物燒結而得之高導熱性材料。 依據本發明，提供一種半導體裝置，其具備：基材；及半導體元件，其經由接著層裝載於前述基材上，前述接著層為將前述糊狀樹脂組成物燒結而成。 [發明之效果]The present invention can be as follows. According to the present invention, a paste resin composition is provided, which contains: (A) A compound containing (meth)acrylic acid groups, which has more than two functions, and the number of repeating units of a linear or branched oxyalkylene group is 2 or more; and (B) Metal-containing particles, which contain silver-containing particles or copper-containing particles. According to the present invention, there is provided a high thermal conductivity material obtained by sintering the aforementioned paste resin composition. According to the present invention, there is provided a semiconductor device including: a substrate; and a semiconductor element mounted on the substrate via an adhesive layer, the adhesive layer being formed by sintering the paste resin composition. [Effects of Invention]
依據本發明，能夠提供一種糊狀樹脂組成物，藉由適用於半導體元件與基材的接合，能夠得到長期表現出良好的導電性，長期可靠性優異的半導體裝置。According to the present invention, it is possible to provide a paste-like resin composition, which is suitable for bonding a semiconductor element and a substrate, and a semiconductor device that exhibits good electrical conductivity for a long period of time and is excellent in long-term reliability can be obtained.
以下，使用圖式，對本發明的實施形態進行說明。另外，在所有圖式中，對相同的構成要素標註相同的符號，並適當地省略說明。又，只要沒有特別說明，「～」表示「以上」至「以下」。Hereinafter, the embodiments of the present invention will be described using drawings. In addition, in all the drawings, the same constituent elements are denoted by the same reference numerals, and the description is appropriately omitted. Also, as long as there is no special description, "~" means "above" to "below".
本實施形態的糊狀樹脂組成物含有：（A）含（甲基）丙烯醯基之化合物，其具有2官能以上，直鏈或支鏈的氧伸烷基的重複單元數為2以上；及（B）含金屬之粒子，其含有銀粒子或銅粒子。The paste resin composition of this embodiment contains: (A) a compound containing a (meth)acryloyl group, which has two or more functions, and the number of repeating units of the linear or branched oxyalkylene group is 2 or more; and (B) Metal-containing particles, which contain silver particles or copper particles.
[含（甲基）丙烯醯基之化合物（A）] 作為含（甲基）丙烯醯基之化合物（A），只要是具有2官能以上的（甲基）丙烯醯基，直鏈或支鏈的氧伸烷基的重複單元數為2以上之化合物，在能夠發揮本發明的效果之範圍內，能夠並無限定地使用。[Compounds containing (meth)acrylic acid groups (A)] As the (meth)acryloyl group-containing compound (A), as long as it has a (meth)acryloyl group with more than two functions, and the number of repeating units of a linear or branched oxyalkylene group is 2 or more, It can be used without limitation as long as the effects of the present invention can be exhibited.
在本實施形態中，藉由使用含有具備該結構之含（甲基）丙烯醯基之化合物（A）之糊狀樹脂組成物，燒結該組成物而得之材料的應力得到緩和，韌性亦優異（斷裂能量高，難以斷裂）。因此可以認為，藉由本實施形態的糊狀樹脂組成物接合了半導體元件與基材之半導體裝置可以抑制接合部的剥離等，長期表現出良好的導電性，長期可靠性優異。In this embodiment, by using a paste-like resin composition containing the (meth)acrylic group-containing compound (A) having the structure, the stress of the material obtained by sintering the composition is relieved and the toughness is also excellent (The breaking energy is high and it is difficult to break). Therefore, it is considered that the semiconductor device in which the semiconductor element and the base material are joined by the paste resin composition of the present embodiment can suppress the peeling of the joined portion, etc., exhibit good conductivity for a long time, and have excellent long-term reliability.
從本發明的效果的觀點而言，氧伸烷基的重複單元數能夠設為2以上，較佳為4以上，更佳為4～30，特佳為8～30。From the viewpoint of the effect of the present invention, the number of repeating units of the oxyalkylene group can be set to 2 or more, preferably 4 or more, more preferably 4-30, and particularly preferably 8-30.
作為氧伸烷基，可舉出直鏈或支鏈的碳數2～10的氧伸烷基，較佳為直鏈或支鏈的碳數2～8的氧伸烷基，更佳為直鏈或支鏈的碳數2～5的氧伸烷基。 在本實施形態中，含（甲基）丙烯醯基之化合物（A）含有選自由下述通式（1）表示的化合物中之至少一種為較佳。Examples of the oxyalkylene group include straight-chain or branched oxyalkylene groups having 2 to 10 carbon atoms, preferably straight-chain or branched oxyalkylene groups having 2-8 carbon atoms, and more preferably straight-chain or branched oxyalkylene groups having 2 to 8 carbon atoms. Chain or branched oxyalkylene group having 2 to 5 carbon atoms. In this embodiment, it is preferable that the (meth)acryloyl group-containing compound (A) contains at least one compound selected from the group consisting of compounds represented by the following general formula (1).
通式（1）中，R表示氫原子或碳數1～3的烷基，存在複數個之R可以相同亦可以不同。 X表示氫原子、鹵素原子、羥基、胺基、氰基、巰基、羧基、碳數1～3的烷基或碳數1～3的烷氧基，較佳為氫原子或碳數1～3的烷基。存在複數個之X可以相同亦可以不同。 m能夠表示2～10的整數，較佳為2～8的整數，更佳為2～5的整數。 n能夠表示4以上且30以下的整數，較佳為表示8以上且30以下的整數。In the general formula (1), R represents a hydrogen atom or an alkyl group having 1 to 3 carbons, and a plurality of Rs may be the same or different. X represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a mercapto group, a carboxyl group, an alkyl group having 1 to 3 carbons or an alkoxy group having 1 to 3 carbons, preferably a hydrogen atom or a carbon number of 1 to 3的alkyl. A plurality of Xs may be the same or different. m can represent the integer of 2-10, Preferably it is an integer of 2-8, More preferably, it is an integer of 2-5. n can represent an integer of 4 or more and 30 or less, and preferably represents an integer of 8 or more and 30 or less.
作為含（甲基）丙烯醯基之化合物（A），可舉出二乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲基）丙烯酸酯、聚乙二醇#200二（甲基）丙烯酸酯（n：4）、聚乙二醇#400二（甲基）丙烯酸酯（n：9）、聚乙二醇#600二（甲基）丙烯酸酯（n：14）、聚乙二醇#1000二（甲基）丙烯酸酯（n：23）等。As the (meth)acrylic acid group-containing compound (A), diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol #200bis( Meth) acrylate (n: 4), polyethylene glycol #400 di (meth) acrylate (n: 9), polyethylene glycol #600 di (meth) acrylate (n: 14), poly Ethylene glycol #1000 di(meth)acrylate (n:23), etc.
從本發明的效果的觀點而言，在糊狀樹脂組成物的全部非揮發性成分中，含（甲基）丙烯醯基之化合物（A）能夠以0.1～15重量%以下，較佳為0.5～10重量%，更佳為1.0～8重量%的量含有。From the viewpoint of the effects of the present invention, the (meth)acrylic acid group-containing compound (A) can be 0.1 to 15% by weight or less, preferably 0.5 It is contained in an amount of -10% by weight, more preferably 1.0-8% by weight.
另外，在不對本發明的效果產生影響之範圍內，還能夠與含（甲基）丙烯醯基之化合物（A）一起含有在一個分子中僅具備一個（甲基）丙烯醯基之單官能（甲基）丙烯酸單體等除了含（甲基）丙烯醯基之化合物（A）以外的含（甲基）丙烯醯基之化合物。In addition, within the range that does not affect the effect of the present invention, it can also contain a (meth)acryloyl group-containing compound (A) together with a monofunctional (meth)acryloyl group having only one (meth)acryloyl group in one molecule ( (Meth)acrylic acid monomers and other (meth)acrylic acid group-containing compounds other than (meth)acrylic acid group-containing compound (A).
[含金屬之粒子（B）] 含金屬之粒子（B）能夠藉由適當的熱處理而發生燒結（sintering），形成粒子連結結構（燒結結構）。 含金屬之粒子（B）能夠含有含銀粒子或含銅粒子。[Metal-containing particles (B)] The metal-containing particles (B) can be sintered by appropriate heat treatment to form a particle connection structure (sintered structure). The metal-containing particles (B) can contain silver-containing particles or copper-containing particles.
尤其，藉由在糊狀樹脂組成物中含有含銀粒子（尤其，藉由含有粒徑相對小且比表面積相對大的銀粒子），即使在相對低溫（180℃左右）中進行熱處理亦容易形成燒結結構。較佳之粒徑留待後述。In particular, by containing silver-containing particles in the paste resin composition (especially, by containing silver particles with a relatively small particle size and a relatively large specific surface area), it is easy to form even if it is heat-treated at a relatively low temperature (around 180°C) Sintered structure. The preferred particle size will be described later.
含金屬之粒子（B）的形狀並無特別限定。較佳之形狀為球狀，但是亦可以為非球狀的形狀，例如橢圓體狀、扁平狀、板狀、片（flake）狀、針狀等。 （「球狀」並不限於完美的真球，還包括表面上帶有些許凹凸之形狀等。以下，在本說明書中同樣適用。）The shape of the metal-containing particles (B) is not particularly limited. The preferred shape is spherical, but it can also be aspherical, such as ellipsoid, flat, plate, flake, needle, etc. (The "spherical shape" is not limited to a perfect real ball, but also includes a shape with a little unevenness on the surface, etc. The following applies in this manual as well.)
含金屬之粒子（B）可以為（i）實質上僅由金屬構成之粒子，亦可以為（ii）由金屬和金屬以外的成分構成之粒子。又，作為含金屬之粒子，亦可以併用（i）及（ii）。The metal-containing particles (B) may be (i) particles substantially composed of metal only, or (ii) particles composed of metal and components other than metals. In addition, as metal-containing particles, (i) and (ii) may be used in combination.
在本實施形態中，含金屬之粒子（B）包含樹脂粒子的表面被金屬塗覆之金屬塗層樹脂粒子為特佳。藉此，能夠製備得到導熱性更優異且儲存彈性模數更優異的硬化物之糊狀樹脂組成物。In this embodiment, the metal-containing particles (B) include metal-coated resin particles whose surfaces are coated with a metal and resin particles are particularly preferred. Thereby, it is possible to prepare a paste-like resin composition of a cured product having more excellent thermal conductivity and a more excellent storage elastic modulus.
金屬塗層樹脂粒子的表面為金屬，且其內部為樹脂，因此導熱性良好，且與僅由金屬構成之粒子相比柔軟。因此，藉由使用金屬塗層樹脂粒子，能夠容易將導熱率或儲存彈性模數設計為適當的值。The surface of the metal-coated resin particle is metal, and the inside is resin, so it has good thermal conductivity and is softer than particles composed only of metal. Therefore, by using metal-coated resin particles, the thermal conductivity or storage elastic modulus can be easily designed to an appropriate value.
通常，為了提高導熱性，可考慮增加含金屬之粒子的量。然而，通常，由於金屬「堅硬」，因此若含金屬之粒子的量過多，則燒結後的彈性模數有時會變得過大。藉由含金屬之粒子的一部分或全部為金屬塗層樹脂粒子，能夠容易設計能夠得到具有所期望的導熱率或儲存彈性模數之硬化物之糊狀樹脂組成物。Generally, in order to improve thermal conductivity, it is considered to increase the amount of metal-containing particles. However, in general, since the metal is "hard", if the amount of metal-containing particles is too large, the elastic modulus after sintering may sometimes become too large. When part or all of the metal-containing particles are metal-coated resin particles, it is possible to easily design a paste-like resin composition that can obtain a cured product having a desired thermal conductivity or storage elastic modulus.
在金屬塗層樹脂粒子中，金屬層只要覆蓋樹脂粒子的表面的至少一部分區域即可。當然，金屬亦可以覆蓋樹脂粒子的整個表面。In the metal-coated resin particle, the metal layer only needs to cover at least a part of the surface of the resin particle. Of course, the metal can also cover the entire surface of the resin particles.
具體而言，在金屬塗層樹脂粒子中，金屬層覆蓋樹脂粒子的表面的50%以上為較佳，更佳為75%以上，進一步較佳為90%以上。在金屬塗層樹脂粒子中，金屬層實質上覆蓋樹脂粒子的整個表面為特佳。 作為另一觀點，當用某一剖面切斷金屬塗層樹脂粒子時，在該剖面的周圍皆可確認金屬層為較佳。Specifically, in the metal-coated resin particles, it is preferable that the metal layer covers 50% or more of the surface of the resin particle, more preferably 75% or more, and still more preferably 90% or more. In the metal-coated resin particles, it is particularly preferable that the metal layer covers substantially the entire surface of the resin particles. As another point of view, when the metal-coated resin particles are cut with a certain cross-section, it can be confirmed that the metal layer is preferably around the cross-section.
作為又一觀點，金屬塗層樹脂粒子中的樹脂/金屬的質量比率例如為90/10～10/90，較佳為80/20～20/80，更佳為70/30～30/70。As another viewpoint, the mass ratio of resin/metal in the metal-coated resin particles is, for example, 90/10 to 10/90, preferably 80/20 to 20/80, and more preferably 70/30 to 30/70.
金屬塗層樹脂粒子中的「金屬」如上所述。尤其，銀為較佳。 作為金屬塗層樹脂粒子中的「樹脂」，例如可舉出聚矽氧樹脂、（甲基）丙烯酸樹脂、酚樹脂、聚苯乙烯樹脂、三聚氰胺樹脂、聚醯胺樹脂、聚四氟乙烯樹脂等。當然，亦可以為除此之外的樹脂。又，樹脂可以僅為一種，亦可以併用兩種以上的樹脂。 從彈性特性和耐熱性的觀點而言，樹脂為聚矽氧樹脂或（甲基）丙烯酸樹脂為較佳。The "metal" in the metal-coated resin particles is as described above. In particular, silver is preferred. Examples of the "resin" in the metal-coated resin particles include silicone resins, (meth)acrylic resins, phenol resins, polystyrene resins, melamine resins, polyamide resins, polytetrafluoroethylene resins, etc. . Of course, other resins may also be used. In addition, only one type of resin may be used, or two or more types of resins may be used in combination. From the standpoint of elastic properties and heat resistance, the resin is preferably silicone resin or (meth)acrylic resin.
聚矽氧樹脂可以為由有機聚矽氧烷構成之粒子，該有機聚矽氧烷藉由使甲基氯矽烷、三甲基三氯矽烷、二甲基二氯矽烷等有機氯矽烷聚合而得。又，亦可以為以將有機聚矽氧烷進一步三維交聯而成之結構為基本骨架之聚矽氧樹脂。Polysiloxane resin can be particles composed of organopolysiloxane, which is obtained by polymerizing organochlorosilane such as methylchlorosilane, trimethyltrichlorosilane, dimethyldichlorosilane, etc. . In addition, it may also be a polysiloxane resin having a structure formed by further three-dimensional cross-linking of organopolysiloxane as the basic skeleton.
（甲基）丙烯酸樹脂能夠含有50重量%以上，較佳為70重量%以上，更佳為90重量%以上使含（甲基）丙烯酸酯之單體聚合而得之樹脂作為主成分。作為（甲基）丙烯酸酯，例如可舉出選自由（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸硬脂酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-丙酯、（甲基）丙烯酸氯-2-羥乙酯、單（甲基）丙烯酸二乙二醇酯、（甲基）丙烯酸甲氧基乙酯、（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸二環戊酯、（甲基）丙烯酸二環戊烯酯及（甲基）丙烯酸異莰酯組成之群中之至少一種化合物。又，丙烯酸系樹脂的單體成分可以含有少量的其他單體。作為該等其他單體成分，例如可舉出苯乙烯系單體。關於金屬塗層（甲基）丙烯酸樹脂，亦可以參閱日本特開2017-126463號公報的記載等。The (meth)acrylic resin can contain 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, as a main component of a resin obtained by polymerizing a (meth)acrylate-containing monomer. Examples of (meth)acrylates include those selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. 2-ethylhexyl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-Propyl ester, chloro-2-hydroxyethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate , At least one compound in the group consisting of dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate. In addition, the monomer component of the acrylic resin may contain a small amount of other monomers. Examples of these other monomer components include styrene-based monomers. Regarding the metal coating (meth)acrylic resin, you can also refer to the description in JP 2017-126463 A, etc.
可以在聚矽氧樹脂或（甲基）丙烯酸樹脂中導入各種官能基。可導入之官能基並無特別限定。例如可舉出環氧基、胺基、甲氧基、苯基、羧基、羥基、烷基、乙烯基、巰基等。Various functional groups can be introduced into silicone resin or (meth)acrylic resin. The functional groups that can be introduced are not particularly limited. For example, an epoxy group, an amino group, a methoxy group, a phenyl group, a carboxyl group, a hydroxyl group, an alkyl group, a vinyl group, a mercapto group, etc. can be mentioned.
金屬塗層樹脂粒子中的樹脂粒子的部分可以含有各種添加成分，例如低應力改質劑等。作為低應力改質劑，可舉出丁二烯苯乙烯橡膠、丁二烯丙烯腈橡膠、聚胺酯（polyurethane）橡膠、聚異戊二烯橡膠、丙烯酸橡膠、氟橡膠、液態有機聚矽氧烷、液態聚丁二烯等液態合成橡膠等。尤其，在樹脂粒子的部分含有聚矽氧樹脂之情況下，藉由含有低應力改質劑，能夠使金屬塗層樹脂粒子的彈性特性成為較佳者。The part of the resin particles in the metal-coated resin particles may contain various additional components, such as low-stress modifiers. Examples of low-stress modifiers include butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluorine rubber, liquid organopolysiloxane, Liquid synthetic rubber such as liquid polybutadiene, etc. In particular, in the case where the part of the resin particles contains silicone resin, by containing a low-stress modifier, the elastic properties of the metal-coated resin particles can be improved.
金屬塗層樹脂粒子中的樹脂粒子的部分的形狀並無特別限定。較佳之形狀為球狀，但是亦可以為球狀以外的不同形狀，例如扁平狀、板狀、針狀等。在將金屬塗層樹脂粒子的形狀形成為球狀之情況下，所使用之樹脂粒子的形狀亦係球狀為較佳。The shape of the part of the resin particle in the metal-coated resin particle is not particularly limited. The preferred shape is spherical, but different shapes other than spherical, such as flat shape, plate shape, needle shape, etc., can also be used. In the case of forming the shape of the metal-coated resin particles into a spherical shape, the shape of the resin particles used is also preferably a spherical shape.
金屬塗層樹脂粒子的比重並無特別限定，下限例如為2以上，較佳為2.5以上，更佳為3以上。又，比重的上限例如為10以下，較佳為9以下，更佳為8以下。適當的比重在金屬塗層樹脂粒子本身的分散性、或併用金屬塗層樹脂粒子及除此之外的含金屬之粒子時的均勻性等方面較佳。The specific gravity of the metal-coated resin particles is not particularly limited, and the lower limit is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. In addition, the upper limit of the specific gravity is, for example, 10 or less, preferably 9 or less, and more preferably 8 or less. The appropriate specific gravity is preferable in terms of the dispersibility of the metal-coated resin particles themselves, or the uniformity when the metal-coated resin particles and other metal-containing particles are used in combination.
在使用金屬塗層樹脂粒子之情況下，整個含金屬之粒子（B）中的金屬塗層樹脂粒子的比例較佳為1～50質量%，更佳為3～45質量%，進一步較佳為5～40質量%。藉由適當地調整該比例，能夠在抑制熱循環所致之接著力降低的同時，進一步提高散熱性。In the case of using metal-coated resin particles, the proportion of metal-coated resin particles in the entire metal-containing particles (B) is preferably 1-50% by mass, more preferably 3-45% by mass, and still more preferably 5-40% by mass. By appropriately adjusting the ratio, it is possible to further improve heat dissipation while suppressing the decrease in adhesive force caused by thermal cycling.
順帶一提，在整個含金屬之粒子（B）中的金屬塗層樹脂粒子的比例不是100質量%之情況下，金屬塗層樹脂粒子以外的含金屬之粒子例如為實質上僅由金屬構成之粒子。Incidentally, when the proportion of the metal-coated resin particles in the metal-containing particles (B) is not 100% by mass, the metal-containing particles other than the metal-coated resin particles are, for example, substantially composed of only metal. particle.
含金屬之粒子（B）（在併用複數種含金屬之粒子之情況下為整體）的中值粒徑D50 例如為0.001～1000μm，較佳為0.01～100μm，更佳為0.1～20μm。藉由將D50 設為適當的值，容易保持導熱性、燒結性、對熱循環之耐性等的平衡。又，藉由將D50 設為適當的值，有時亦可提高塗佈/接著的作業性。 含金屬之粒子的粒度分布（橫軸：粒徑、縱軸：頻率）可以為單峰性，亦可以為多峰性。 The median particle diameter D 50 of the metal-containing particles (B) (when a plurality of metal-containing particles are used in combination) is, for example, 0.001 to 1000 μm, preferably 0.01 to 100 μm, and more preferably 0.1 to 20 μm. By setting D 50 to an appropriate value, it is easy to maintain the balance of thermal conductivity, sinterability, resistance to thermal cycles, and the like. In addition, by setting D 50 to an appropriate value, the workability of coating/adhesiveness may be improved in some cases. The particle size distribution (horizontal axis: particle size, vertical axis: frequency) of metal-containing particles can be unimodal or multimodal.
實質上僅由金屬構成之粒子的中值粒徑D50 例如為0.8μm以上，較佳為1.0μm以上，更佳為1.2μm以上。藉此，能夠進一步提高導熱性。 The median diameter D 50 of the particles substantially composed of only metal is, for example, 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. Thereby, the thermal conductivity can be further improved.
又，實質上僅由金屬構成之粒子的中值粒徑D50 例如為7.0μm以下，較佳為5.0μm以下，更佳為4.0μm以下。藉此，能夠進一步提高易燒結性和燒結的均勻性等。 In addition, the median diameter D 50 of particles substantially composed of only metal is, for example, 7.0 μm or less, preferably 5.0 μm or less, and more preferably 4.0 μm or less. Thereby, it is possible to further improve the ease of sintering, the uniformity of sintering, and the like.
含金屬之粒子（B）的中值粒徑D50 例如為0.5μm以上，較佳為1.5μm以上，更佳為2.0μm以上。藉此，容易將儲存彈性模數E’設為適當的值。 The median diameter D 50 of the metal-containing particles (B) is, for example, 0.5 μm or more, preferably 1.5 μm or more, and more preferably 2.0 μm or more. Thereby, it is easy to set the storage elastic modulus E'to an appropriate value.
又，含金屬之粒子（B）的中值粒徑D50 例如為20μm以下，較佳為15μm以下，更佳為10μm以下。藉此，容易充分提高導熱性。 In addition, the median diameter D 50 of the metal-containing particles (B) is, for example, 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less. Thereby, it is easy to sufficiently improve the thermal conductivity.
含金屬之粒子（B）的中值粒徑D50 例如可以藉由使用Sysmex Corporation製流動式粒子像分析裝置FPIA（註冊商標）-3000進行粒子影像測量來求出。更具體而言，可以藉由使用該裝置以濕式測量體積基準的中值粒徑來確定含金屬之粒子（B）的粒徑。 The median diameter D 50 of the metal-containing particles (B) can be determined by, for example, performing particle image measurement using a flow-type particle image analyzer FPIA (registered trademark)-3000 manufactured by Sysmex Corporation. More specifically, the particle size of the metal-containing particles (B) can be determined by using the device to measure the median particle size on a volume basis in a wet type.
整個糊狀樹脂組成物中的含金屬之粒子（B）（在使用複數種含金屬之粒子之情況下為該等的總計）的比例例如為1～98質量%，較佳為30～95質量%，更佳為50～90質量%。藉由將含金屬之粒子的比例設為1質量%以上，容易提高導熱性。藉由將含金屬之粒子（B）的比例設為98質量%以下，能夠提高塗佈/接著的作業性。The ratio of the metal-containing particles (B) (in the case of using plural kinds of metal-containing particles) in the entire paste resin composition is, for example, 1 to 98% by mass, preferably 30 to 95% by mass %, more preferably 50 to 90% by mass. By setting the ratio of the metal-containing particles to 1% by mass or more, it is easy to improve the thermal conductivity. By setting the ratio of the metal-containing particles (B) to 98% by mass or less, the workability of coating/adhesive can be improved.
含金屬之粒子（B）中實質上僅由金屬構成之粒子例如可以從Dowa Hightech Co.,Ltd.、Fukuda Metal Foil & Powder Co.,Ltd.等獲取。又，金屬塗層樹脂粒子例如可以從Mitsubishi Materials Corporation、Sekisui Chemical Co.,Ltd.、Sanno Co.,Ltd.等獲取。Among the metal-containing particles (B), particles that are substantially composed of only metal can be obtained from Dowa Hightech Co., Ltd., Fukuda Metal Foil & Powder Co., Ltd., etc., for example. In addition, the metal-coated resin particles can be obtained from, for example, Mitsubishi Materials Corporation, Sekisui Chemical Co., Ltd., Sanno Co., Ltd., and the like.
[熱固性樹脂（C）] 本實施形態的糊狀樹脂組成物還能夠含有熱固性樹脂（C）。在本實施形態中，熱固性樹脂（C）不包括含（甲基）丙烯醯基之化合物（A）。[Thermosetting resin (C)] The paste resin composition of this embodiment can also contain a thermosetting resin (C). In this embodiment, the thermosetting resin (C) does not include the (meth)acrylic group-containing compound (A).
熱固性樹脂（C）通常含有藉由使自由基等活性化學物種作用而聚合/交聯之基團和/或與後述的硬化劑（D）反應之化學結構。熱固性樹脂（C）例如含有環氧基、氧雜環丁烷基（oxetanyl group）、含有乙烯性碳-碳雙鍵之基團、羥基、異氰酸基、順丁烯二醯亞胺結構等中的一種或兩種以上。 作為熱固性樹脂（C），可較佳地舉出環氧樹脂。 環氧樹脂可以為在一個分子中僅具備一個環氧基之化合物，亦可以為在一個分子中具備兩個以上的環氧基之化合物。The thermosetting resin (C) usually contains a group that is polymerized/crosslinked by the action of active chemical species such as free radicals and/or a chemical structure that reacts with the hardener (D) described later. Thermosetting resin (C), for example, contains epoxy group, oxetanyl group, group containing ethylenic carbon-carbon double bond, hydroxyl group, isocyanate group, maleimide structure, etc. One or two or more of them. As the thermosetting resin (C), preferably, epoxy resin is used. The epoxy resin may be a compound having only one epoxy group in one molecule, or a compound having two or more epoxy groups in one molecule.
作為環氧樹脂，例如可舉出：聯苯基型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、二苯乙烯型環氧樹脂、對苯二酚型環氧樹脂等2官能性或結晶性環氧樹脂；甲酚酚醛清漆型環氧樹脂、酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；含伸苯基骨架之苯酚芳烷基型環氧樹脂、含聯伸苯基（biphenylene）骨架之苯酚芳烷基型環氧樹脂、含伸苯基骨架之萘酚芳烷基型環氧樹脂等苯酚芳烷基型環氧樹脂；三酚甲烷型環氧樹脂及烷基改質三酚甲烷型環氧樹脂等3官能型環氧樹脂；二環戊二烯改質苯酚型環氧樹脂、萜烯改質苯酚型環氧樹脂等改質苯酚型環氧樹脂；含三𠯤核之環氧樹脂等含雜環之環氧樹脂等。Examples of epoxy resins include biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, and hydroquinone type epoxy resins. 2 functional or crystalline epoxy resins; novolac epoxy resins such as cresol novolac epoxy resin, novolac epoxy resin, naphthol novolac epoxy resin, etc.; phenol containing phenylene skeleton Phenol aralkyl type epoxy resins, phenol aralkyl type epoxy resins containing biphenylene skeleton, naphthol aralkyl type epoxy resins containing phenylene skeleton, etc. Resins; trifunctional epoxy resins such as trisphenol methane type epoxy resin and alkyl modified trisphenol methane type epoxy resin; dicyclopentadiene modified phenol type epoxy resin, terpene modified phenol type epoxy resin Modified phenol-based epoxy resins such as resins; epoxy resins containing three nuclei, such as heterocyclic epoxy resins, etc.
又，作為含環氧基之化合物，亦能夠含有4-三級丁基苯基環氧丙基醚、間甲苯酚基環氧丙基醚、對甲苯酚基環氧丙基醚、苯基環氧丙基醚、甲苯酚基環氧丙基醚等單官能的含環氧基之化合物。 本實施形態的糊狀樹脂組成物可以僅含有一種熱固性成分，亦可以含有兩種以上的熱固性成分。In addition, as an epoxy group-containing compound, it can also contain 4-tertiary butyl phenyl glycidyl ether, m-cresol glycidyl ether, p-cresol glycidyl ether, and phenyl ring Monofunctional epoxy-containing compounds such as oxypropyl ether and cresolyl glycidyl ether. The paste resin composition of this embodiment may contain only one type of thermosetting component, or may contain two or more types of thermosetting components.
在本實施形態中，熱固性樹脂（C）與含（甲基）丙烯醯基之化合物（A）併用為較佳。併用該等時的比率（質量比）並無特別限定，例如熱固性樹脂（C）/含（甲基）丙烯醯基之化合物（A）=95/5～50/50，較佳為熱固性樹脂（C）/（含（甲基）丙烯醯基之化合物（A）=90/10～60/40。In this embodiment, the thermosetting resin (C) and the (meth)acrylic acid group-containing compound (A) are preferably used in combination. The ratio (mass ratio) when these are used in combination is not particularly limited. For example, thermosetting resin (C)/(meth)acryloyl group-containing compound (A)=95/5-50/50, preferably thermosetting resin ( C)/(Compound containing (meth)acryloyl group (A)=90/10～60/40.
作為熱固性樹脂（C），環氧樹脂為較佳。作為環氧樹脂，可較佳地舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂等。 本實施形態的糊狀樹脂組成物中的熱固性樹脂（C）的量在全部非揮發性成分中，例如為3～20質量%，較佳為5～15質量%。As the thermosetting resin (C), epoxy resin is preferred. As the epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and the like are preferably used. The amount of the thermosetting resin (C) in the paste resin composition of the present embodiment is, for example, 3 to 20% by mass, preferably 5 to 15% by mass in all non-volatile components.
[硬化劑（D）] 本實施形態的糊狀樹脂組成物還能夠含有硬化劑（D）。[Hardener (D)] The paste resin composition of this embodiment can further contain a curing agent (D).
作為硬化劑（D），可舉出具有與熱固性樹脂（C）反應之反應性基者。硬化劑（D）例如含有與熱固性樹脂（C）中含有之環氧基、順丁烯二醯亞胺基、羥基等官能基反應之反應性基。Examples of the hardener (D) include those having a reactive group that reacts with the thermosetting resin (C). The hardener (D) contains, for example, a reactive group that reacts with functional groups such as epoxy groups, maleimide groups, and hydroxyl groups contained in the thermosetting resin (C).
硬化劑（D）含有酚系硬化劑和/或咪唑系硬化劑為較佳。該等硬化劑在熱固性成分含有環氧基時為特佳。 酚系硬化劑可以為低分子化合物，亦可以為高分子化合物（亦即，酚樹脂）。The curing agent (D) preferably contains a phenolic curing agent and/or an imidazole curing agent. These hardeners are particularly preferred when the thermosetting component contains an epoxy group. The phenolic hardener may be a low-molecular compound or a high-molecular compound (that is, a phenol resin).
作為低分子化合物之酚系硬化劑，例如可舉出：雙酚A、雙酚F（二羥基二苯甲烷）等雙酚化合物（具有雙酚F骨架之酚樹脂）；4,4’-雙酚等具有聯伸苯基骨架之化合物等。Examples of phenolic hardeners for low-molecular-weight compounds include bisphenol compounds (phenol resins with a bisphenol F skeleton) such as bisphenol A and bisphenol F (dihydroxydiphenylmethane); 4,4'-bis Phenol and other compounds having a biphenylene skeleton, etc.
作為酚樹脂，具體而言，可舉出：酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚酚醛清漆樹脂、苯酚-聯苯酚醛清漆樹脂等酚醛清漆型酚樹脂；聚乙烯苯酚；三苯甲烷型酚樹脂等多官能型酚樹脂；萜烯改質酚樹脂、二環戊二烯改質酚樹脂等改質酚樹脂；具有伸苯基骨架和/或聯伸苯基骨架之苯酚芳烷基樹脂、具有伸苯基和/或聯伸苯基骨架之萘酚芳烷基樹脂等苯酚芳烷基型酚樹脂等。 在使用硬化劑（D）之情況下，可以僅使用一種，亦可以併用兩種以上。Specific examples of the phenol resin include: novolak type phenol resins such as novolak resin, cresol novolak resin, bisphenol novolak resin, phenol-biphenol novolak resin; polyvinyl phenol; triphenylmethane type Polyfunctional phenol resins such as phenol resins; modified phenol resins such as terpene-modified phenol resins and dicyclopentadiene-modified phenol resins; phenol aralkyl resins with phenylene skeleton and/or biphenylene skeleton , Phenol aralkyl type phenol resins such as naphthol aralkyl resin with phenylene and/or biphenylene skeleton. When using the hardener (D), only one type may be used, or two or more types may be used in combination.
在本實施形態的糊狀樹脂組成物含有硬化劑（D）之情況下，當將熱固性樹脂（C）的量設為100質量份時，其量例如為10～150質量份，較佳為20～100質量份。In the case where the paste resin composition of the present embodiment contains the curing agent (D), when the amount of the thermosetting resin (C) is 100 parts by mass, the amount is, for example, 10 to 150 parts by mass, preferably 20 parts by mass. ~100 parts by mass.
（硬化促進劑） 本實施形態的糊狀樹脂組成物還能夠含有硬化促進劑。 典型地，硬化促進劑為促進熱固性樹脂（C）與硬化劑（D）的反應者。(Hardening accelerator) The paste resin composition of this embodiment can also contain a hardening accelerator. Typically, the hardening accelerator is one that promotes the reaction between the thermosetting resin (C) and the hardening agent (D).
作為硬化促進劑，具體而言，可舉出：有機膦、四取代鏻化合物、磷酸酯甜菜鹼（phosphobetaine）化合物、膦化合物和醌化合物的加成物、鏻化合物和矽烷化合物的加成物等含有磷原子之化合物；二氰二胺、1,8-二氮雜二環[5.4.0]十一烯-7、苄基二甲胺等脒、三級胺；上述脒或上述三級胺的四級銨鹽等含有氮原子之化合物等。 在使用硬化促進劑之情況下，可以僅使用一種，亦可以併用兩種以上。Specific examples of hardening accelerators include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, etc. Compounds containing phosphorus atoms; dicyandiamine, 1,8-diazabicyclo[5.4.0]undecene-7, benzyldimethylamine and other amidines, tertiary amines; the above-mentioned amidines or the above-mentioned tertiary amines The quaternary ammonium salt and other compounds containing nitrogen atoms. In the case of using a hardening accelerator, only one type may be used, or two or more types may be used in combination.
在本實施形態的糊狀樹脂組成物含有硬化促進劑之情況下，當將熱固性樹脂（C）的量設為100質量份時，其量例如為0.1～10質量份，較佳為0.5～5質量份。When the paste resin composition of the present embodiment contains a curing accelerator, when the amount of the thermosetting resin (C) is 100 parts by mass, the amount is, for example, 0.1-10 parts by mass, preferably 0.5-5 parts by mass. Mass parts.
（矽烷偶合劑） 本實施形態的糊狀樹脂組成物還能夠含有矽烷偶合劑。藉此，能夠實現接著力的進一步提高。(Silane coupling agent) The paste resin composition of this embodiment can also contain a silane coupling agent. With this, it is possible to further improve the adhesive force.
作為矽烷偶合劑，可舉出公知的矽烷偶合劑，具體而言，可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等乙烯基矽烷； 2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷等環氧矽烷； 對苯乙烯基三甲氧基矽烷等苯乙烯基矽烷； 3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等甲基丙烯醯基矽烷； 甲基丙烯酸3-（三甲氧基矽基）丙酯、3-丙烯醯氧基丙基三甲氧基矽烷等丙烯酸矽烷； N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-γ-胺基丙基三甲氧基矽烷等胺基矽烷； 三聚異氰酸基矽烷； 烷基矽烷； 3-脲基丙基三烷氧基矽烷等脲基矽烷； 3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等巰基矽烷； 3-異氰酸基丙基三乙氧基矽烷等異氰酸基矽烷等。 在使用矽烷偶合劑之情況下，可以僅使用一種，亦可以併用兩種以上。As the silane coupling agent, a well-known silane coupling agent can be mentioned. Specifically, vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxy silane can be mentioned; 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl dimethoxy silane, Silicone oxide such as 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.; Styryl silane such as p-styryl trimethoxy silane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-methacryloxypropyltriethoxysilane and other methacryloxysilanes; Acrylic silanes such as 3-(trimethoxysilyl)propyl methacrylate, 3-propenyloxypropyltrimethoxysilane, etc.; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-amine Propyl propyl trimethoxysilane, 3-aminopropyl triethoxy silane, 3-triethoxy silyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl- Aminosilanes such as γ-aminopropyltrimethoxysilane; Trimeric isocyanatosilane; Alkyl Silane; Urea-based silanes such as 3-ureidopropyl trialkoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and other mercaptosilanes; Isocyanatosilanes such as 3-isocyanatopropyltriethoxysilane, etc. When using a silane coupling agent, only one type may be used, or two or more types may be used in combination.
在本實施形態的糊狀樹脂組成物含有矽烷偶合劑之情況下，當將熱固性成分的量（含（甲基）丙烯醯基之化合物（A）及熱固性樹脂（C）的總計量）設為100質量份時，其量例如為0.1～10質量份，較佳為0.5～5質量份。When the paste resin composition of this embodiment contains a silane coupling agent, the amount of the thermosetting component (the total amount of the (meth)acryloyl group-containing compound (A) and the thermosetting resin (C)) is set to At 100 parts by mass, the amount is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass.
（塑化劑） 本實施形態的糊狀樹脂組成物能夠含有塑化劑。藉由塑化劑，容易將儲存彈性模數設計得較小。又，容易進一步抑制熱循環所致之接著力降低。(Plasticizer) The paste resin composition of this embodiment can contain a plasticizer. With plasticizer, it is easy to design the storage elastic modulus to be smaller. In addition, it is easy to further suppress the decrease in adhesive force due to thermal cycling.
作為塑化劑，具體而言，可舉出聚酯化合物、聚矽氧油、聚矽氧橡膠等聚矽氧化合物、聚丁二烯順丁烯二酸酐加成物等聚丁二烯化合物、丙烯腈丁二烯共聚化合物等。 在使用塑化劑之情況下，可以僅使用一種，亦可以併用兩種以上。Specific examples of the plasticizer include polysilicon compounds such as polyester compounds, silicone oils and silicone rubbers, polybutadiene compounds such as polybutadiene maleic anhydride adducts, Acrylonitrile butadiene copolymer compound, etc. When using a plasticizer, only one kind may be used, or two or more kinds may be used in combination.
在本實施形態的糊狀樹脂組成物含有塑化劑之情況下，當將熱固性成分的量（含（甲基）丙烯醯基之化合物（A）及熱固性樹脂（C）的總計量）設為100質量份時，其量例如為5～50質量份，較佳為10～30質量份。When the paste resin composition of this embodiment contains a plasticizer, the amount of the thermosetting component (the total amount of the (meth)acryloyl group-containing compound (A) and the thermosetting resin (C)) is At 100 parts by mass, the amount is, for example, 5 to 50 parts by mass, and preferably 10 to 30 parts by mass.
（自由基起始劑） 本實施形態的糊狀樹脂組成物能夠含有自由基起始劑。 藉由自由基起始劑，例如有時能夠抑制硬化不充分，或能夠在相對低溫（例如180℃）時充分進行硬化反應，或能夠進一步提高接著力。 作為自由基起始劑，可舉出過氧化物、偶氮化合物等。(Free radical initiator) The paste resin composition of this embodiment can contain a radical initiator. With the radical initiator, for example, insufficient hardening can be suppressed, or the hardening reaction can be sufficiently advanced at a relatively low temperature (for example, 180° C.), or the adhesive force can be further improved. Examples of the radical initiator include peroxides, azo compounds, and the like.
作為過氧化物，例如可舉出二醯基過氧化物、二烷基過氧化物、過氧化縮酮等有機過氧化物，更具體而言，可舉出甲乙酮過氧化物、環己酮過氧化物等酮過氧化物；1,1-二（三級丁基過氧化）環己烷、2,2-二（4,4-二（三級丁基過氧化）環己基）丙烷等過氧化縮酮； 對薄荷烷氫過氧化物、二異丙基苯氫過氧化物、1,1,3,3-四甲基丁基氫過氧化物、異丙苯氫過氧化物、三級丁基氫過氧化物等氫過氧化物； 二（2-三級丁基過氧異丙基）苯、雙異苯丙基過氧化物、2,5-二甲基-2,5-二（三級丁基過氧）己烷、三級丁基異丙基苯基過氧化物、二-三級己基過氧化物、2,5-二甲基-2,5-二（三級丁基過氧）己炔-3、二-三級丁基過氧化物等二烷基過氧化物； 二苯甲醯基過氧化物、二（4-甲基苯甲醯基）過氧化物等二醯基過氧化物； 二正丙基過氧二碳酸酯、二異丙基過氧二碳酸酯等過氧二碳酸酯； 2,5-二甲基-2,5-二（苯甲醯基過氧）己烷、三級己基過氧苯甲酸酯、三級丁基過氧苯甲酸酯、三級丁基過氧2-乙基己酸酯等過氧酯等。Examples of peroxides include organic peroxides such as diacyl peroxides, dialkyl peroxides, and peroxyketals. More specifically, they include methyl ethyl ketone peroxide and cyclohexanone peroxide. Oxide and other ketone peroxides; 1,1-bis(tertiary butyl peroxide) cyclohexane, 2,2-bis(4,4-bis(tertiary butyl peroxide) cyclohexyl) propane, etc. Oxidized ketal P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tertiary butyl hydroperoxide Hydroperoxides such as oxides; Bis(2-tertiary butylperoxyisopropyl)benzene, bisisophenylpropyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butylperoxy)hexane, three Grade butyl isopropyl phenyl peroxide, di-tertiary hexyl peroxide, 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexyne-3, di-tri Dialkyl peroxides such as butyl peroxide; Dibenzyl peroxide, bis(4-methylbenzyl) peroxide, etc.; Peroxy dicarbonate such as di-n-propyl peroxy dicarbonate and diisopropyl peroxy dicarbonate; 2,5-Dimethyl-2,5-bis(benzylperoxy)hexane, tertiary hexylperoxybenzoate, tertiary butylperoxybenzoate, tertiary butylperoxybenzoate Peroxy esters such as 2-ethylhexanoate and the like.
作為偶氮化合物，可舉出2,2’-偶氮二（4-甲氧基-2,4-二甲基戊腈）、2,2’-偶氮二（2-環丙基丙腈）、2,2’-偶氮二（2,4-二甲基戊腈）等。 在使用自由基起始劑之情況下，可以僅使用一種，亦可以併用兩種以上。As the azo compound, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile) ), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. When using a radical initiator, only one kind may be used, or two or more kinds may be used in combination.
在本實施形態的糊狀樹脂組成物含有自由基起始劑之情況下，當將熱固性成分的量（含（甲基）丙烯醯基之化合物（A）及熱固性樹脂（C）的總計量）設為100質量份時，其量例如為0.1～10質量份，較佳為0.5～8質量份，進一步較佳為0.5～5質量份。When the paste resin composition of this embodiment contains a radical initiator, the amount of the thermosetting component (the total amount of the (meth)acryloyl group-containing compound (A) and the thermosetting resin (C)) When it is set to 100 parts by mass, the amount is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 8 parts by mass, and more preferably 0.5 to 5 parts by mass.
（溶劑） 本實施形態的糊狀樹脂組成物還能夠含有溶劑。藉由溶劑，例如能夠實現調整糊狀樹脂組成物的流動性，提高在基材上形成接著層時的作業性等。(Solvent) The paste resin composition of this embodiment can also contain a solvent. With the solvent, for example, the fluidity of the paste resin composition can be adjusted, and the workability when forming the adhesive layer on the substrate can be improved.
典型地，溶劑為有機溶劑。 作為有機溶劑，可舉出甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、甲基甲氧基丁醇、α-萜品醇、β-萜品醇、己二醇、苄醇、2-苯乙醇、異棕櫚醇、異硬脂醇、月桂醇、乙二醇、丙二醇、丁基丙三醇、丙三醇等醇類； 丙酮、甲基乙基酮、甲基異丁基酮、環己酮、二丙酮醇（4-羥基-4-甲基-2-戊酮）、2-辛酮、異佛酮（3,5,5-三甲基-2-環己烯-1-酮）、二異丁基酮（2,6-二甲基-4-庚酮）等酮類； 乙酸乙酯、乙酸丁酯、鄰苯二甲酸二乙酯、鄰苯二甲酸二丁酯、乙醯氧基乙烷、丁酸甲酯、己酸甲酯、辛酸甲酯、癸酸甲酯、乙酸甲賽璐蘇、乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯、1,2-二乙醯氧基乙烷、磷酸三丁酯、磷酸三甲苯酯、磷酸三戊酯等酯類； 四氫呋喃、二丙醚、乙二醇二甲醚、乙二醇二***、乙二醇二丁醚、丙二醇二甲醚、乙氧基***、1,2-雙（2-二乙氧基）乙烷、1,2-雙（2-甲氧基乙氧基）乙烷等醚類； 乙酸2-（2-丁氧基乙氧基）乙烷等酯醚類； 2-（2-甲氧基乙氧基）乙醇等醚醇類； 甲苯、二甲苯、正烷烴、異烷烴、十二烷基苯、松節油、煤油、輕油等烴類； 乙腈或丙腈等腈類； 乙醯胺、N,N-二甲基甲醯胺等醯胺類； 低分子量的揮發性矽油、揮發性有機改質矽油等矽油類等。 在使用溶劑之情況下，可以僅使用一種溶劑，亦可以併用兩種以上的溶劑。Typically, the solvent is an organic solvent. Examples of organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether. , Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl methoxybutanol, α-terpineol, β-terpineol, hexylene glycol , Benzyl alcohol, 2-phenylethanol, isopalmityl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, butyl glycerol, glycerol and other alcohols; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5 ,5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone) and other ketones; Ethyl acetate, butyl acetate, diethyl phthalate, dibutyl phthalate, acetoxyethane, methyl butyrate, methyl caproate, methyl octanoate, methyl decanoate, Methyl cellulose acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 1,2-diethoxyethane, tributyl phosphate, tricresyl phosphate, tripentyl phosphate And other esters; Tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis(2-diethoxy)ethane Ethers such as alkane, 1,2-bis(2-methoxyethoxy)ethane; Acetic acid 2-(2-butoxyethoxy)ethane and other ester ethers; Ether alcohols such as 2-(2-methoxyethoxy)ethanol; Toluene, xylene, normal alkanes, isoalkanes, dodecylbenzene, turpentine, kerosene, light oil and other hydrocarbons; Nitriles such as acetonitrile or propionitrile; Acetamide, N,N-dimethylformamide and other amides; Low molecular weight volatile silicone oil, volatile organic modified silicone oil and other silicone oils. When using a solvent, only one solvent may be used, or two or more solvents may be used in combination.
在使用溶劑之情況下，其量並無特別限定。只要基於所期望的流動性等適當調整使用量即可。作為一例，以使糊狀樹脂組成物的非揮發性成分濃度成為50～90質量%之量使用溶劑。In the case of using a solvent, its amount is not particularly limited. It is sufficient to appropriately adjust the usage amount based on the desired fluidity and the like. As an example, the solvent is used in such an amount that the non-volatile component concentration of the paste resin composition becomes 50 to 90% by mass.
（組成物的性狀） 本實施形態的糊狀樹脂組成物較佳為在20℃時為糊狀。亦即，本實施形態的糊狀樹脂組成物可以在20℃時如漿糊般塗佈於基板等為較佳。藉此，能夠將本實施形態的糊狀樹脂組成物較佳地用作半導體元件的接著劑等。 當然，依據所適用之製程等，本實施形態的糊狀樹脂組成物亦可以為相對低黏度的清漆狀等。(Properties of the composition) The paste resin composition of the present embodiment is preferably in a paste form at 20°C. That is, it is preferable that the paste resin composition of the present embodiment can be applied to a substrate or the like like a paste at 20°C. Thereby, the paste resin composition of this embodiment can be suitably used as an adhesive agent etc. of a semiconductor element. Of course, the paste-like resin composition of this embodiment may also be in the form of a relatively low-viscosity varnish, etc., depending on the applicable manufacturing process and the like.
＜高導熱性材料＞ 能夠藉由燒結本實施形態的糊狀樹脂組成物來得到高導熱性材料。 藉由改變高導熱性材料的形狀，能夠適用於在汽車、電機領域中需要散熱性之各種零件。＜High thermal conductivity material＞ A material with high thermal conductivity can be obtained by sintering the paste resin composition of this embodiment. By changing the shape of the high thermal conductivity material, it can be applied to various parts that require heat dissipation in the fields of automobiles and motors.
＜半導體裝置＞ 能夠使用本實施形態的糊狀樹脂組成物來製造半導體裝置。例如，藉由將本實施形態的糊狀樹脂組成物用作基材和半導體元件的「接著劑」，能夠製造半導體裝置。＜Semiconductor device＞ The paste resin composition of this embodiment can be used to manufacture a semiconductor device. For example, a semiconductor device can be manufactured by using the paste resin composition of this embodiment as a base material and an "adhesive agent" of a semiconductor element.
換言之，本實施形態的半導體裝置例如具備：基材；及半導體元件，其經由藉由熱處理將上述糊狀樹脂組成物燒結而得之接著層裝載於基材上。 本實施形態的半導體裝置中，接著層的密接性等亦不易因熱循環而降低。亦即，本實施形態的半導體裝置的可靠性高。 作為半導體元件，可舉出IC、LSI、電力用半導體元件（功率半導體）、其他各種元件。 作為基板，可舉出各種半導體晶圓、引線框、BGA基板、安裝基板、散熱片（heat spreader）、散熱裝置（heat sink）等。In other words, the semiconductor device of the present embodiment includes, for example, a substrate; and a semiconductor element on which an adhesive layer obtained by sintering the above-mentioned paste resin composition by heat treatment is mounted on the substrate. In the semiconductor device of the present embodiment, the adhesiveness of the adhesive layer and the like are also less likely to be reduced due to thermal cycling. That is, the semiconductor device of this embodiment has high reliability. Examples of semiconductor elements include ICs, LSIs, power semiconductor elements (power semiconductors), and various other elements. Examples of the substrate include various semiconductor wafers, lead frames, BGA substrates, mounting substrates, heat spreaders, heat sinks, and the like.
以下，參閱圖式對半導體裝置的一例進行說明。
圖1係表示半導體裝置的一例之剖面圖。
半導體裝置100具備：基材30；及半導體元件20，其經由作為糊狀樹脂組成物的熱處理體之接著層10（晶粒黏著材）裝載於基材30上。Hereinafter, an example of a semiconductor device will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an example of a semiconductor device.
The
半導體元件20和基材30例如經由接合線（bonding wire）40等電連接。又，半導體元件20例如由密封樹脂50密封。The
接著層10的厚度為5μm以上為較佳，10μm以上為更佳，20μm以上為進一步較佳。藉此，能夠提高糊狀樹脂組成物的應力吸收能力，提高耐熱循環性。
接著層10的厚度例如為100μm以下，較佳為50μm以下。The thickness of the
圖1中，基材30例如為引線框。此時，半導體元件20經由接著層10裝載於晶片墊32或基材30上。又，半導體元件20例如經由接合線40與外引線34（基材30）電連接。作為引線框之基材30例如由42合金、Cu框架等構成。In FIG. 1, the
基材30可以為有機基板或陶瓷基板。作為有機基板，例如可舉出由環氧樹脂、氰酸酯樹脂、順丁烯二醯亞胺樹脂等構成者。
基材30的表面例如可以被銀、金等金屬覆蓋。藉此，提高接著層10和基材30的接著性。The
圖2係表示與圖1不同的半導體裝置100的一例之剖面圖。
在圖2的半導體裝置100中，基材30例如為中介層（interposer）。作為中介層之基材30中與裝載有半導體元件20之一面相反的一側的面例如形成複數個焊球52。此時，半導體裝置100經由焊球52與其他配線基板連接。FIG. 2 is a cross-sectional view showing an example of the
對半導體裝置之製造方法的一例進行說明。
首先，將糊狀樹脂組成物塗佈於基材30上，接著，在其上面配置半導體元件20。亦即，依序積層基材30、糊狀樹脂組成物、半導體元件20。
塗佈糊狀樹脂組成物之方法並無特別限定。具體而言，可舉出滴塗法（dispensing）、印刷法、噴墨法等。An example of a method of manufacturing a semiconductor device will be described.
First, the paste-like resin composition is applied on the
接著，使糊狀樹脂組成物熱硬化。熱硬化藉由前硬化及後硬化來進行為較佳。藉由熱硬化，使糊狀樹脂組成物成為熱處理體（硬化物）。藉由熱硬化（熱處理），使糊狀樹脂組成物中的含金屬之粒子凝聚，在接著層10中形成複數個含金屬之粒子彼此的界面消失之結構。藉此，經由接著層10，接著基材30和半導體元件20。接著，使用接合線40，將半導體元件20和基材30電連接。接著，用密封樹脂50密封半導體元件20。如此，能夠製造半導體裝置。Next, the paste resin composition is thermally cured. The thermal hardening is preferably performed by pre-hardening and post-hardening. By thermal curing, the paste resin composition becomes a heat-treated body (cured product). By thermal hardening (heat treatment), the metal-containing particles in the paste resin composition are aggregated to form a structure in which the interface between a plurality of metal-containing particles disappears in the
以上，對本發明的實施形態進行了敘述，但是該等僅為本發明的示例，亦可以採用上述以外的各種構成。又，本發明並不限定於上述實施形態，可實現本發明的目的之範圍內的變形、改良等皆包括在本發明中。 ［實施例］The embodiments of the present invention have been described above, but these are only examples of the present invention, and various configurations other than the above may be adopted. In addition, the present invention is not limited to the above-mentioned embodiments, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention. [Example]
基於實施例及比較例對本發明的實施態樣進行詳細說明。本發明並不限定於實施例。The implementation aspects of the present invention will be described in detail based on examples and comparative examples. The present invention is not limited to the examples.
＜糊狀樹脂組成物的製備＞ 首先，依據後述的表-1所示之摻合量，混合各原料成分，得到清漆。 接著，依據後述的表-1所示之摻合量來摻合得到之清漆、溶劑及含金屬之粒子（含有金屬塗層樹脂粒子），在常溫時用三輥磨機進行了混煉。藉此，製作了糊狀樹脂組成物。<Preparation of Paste Resin Composition> First, according to the blending amount shown in Table-1 described later, the raw material components are mixed to obtain a varnish. Next, the varnish, solvent, and metal-containing particles (containing metal-coated resin particles) were blended according to the blending amounts shown in Table-1 below, and kneaded with a three-roll mill at room temperature. In this way, a paste-like resin composition was produced.
以下，示出表-1的原料成分的資訊。 （熱固性成分） •環氧樹脂1：雙酚F型液態環氧樹脂（Nippon Kayaku Co.,Ltd.製，RE-303S）Below, the information of the raw material composition in Table-1 is shown. (Thermosetting component) •Epoxy resin 1: Bisphenol F type liquid epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE-303S)
（硬化劑） •硬化劑1：具有雙酚F骨架之酚樹脂（在室溫25℃時為固態，DIC Corporation製，DIC-BPF）(hardener) • Hardener 1: Phenolic resin with bisphenol F skeleton (solid at room temperature 25°C, manufactured by DIC Corporation, DIC-BPF)
（含（甲基）丙烯醯基之化合物） •丙烯酸單體1：乙二醇二甲基丙烯酸酯（Kyoeisha Chemical Co.,Ltd.製，LIGHT ESTER EG） •丙烯酸單體2：聚乙二醇#600二甲基丙烯酸酯（通式（1）的n為14）（NOF CORPORATION製，PDE600） •丙烯酸單體3：聚乙二醇#600二甲基丙烯酸酯（通式（1）的n為14）（Kyoeisha Chemical Co.,Ltd.製，LIGHT ESTER 14EG） •丙烯酸單體4：聚乙二醇#1000二丙烯酸酯（通式（1）的n為23）（Shin-Nakamura Chemical Co, Ltd.製，A-1000）(Compounds containing (meth)acrylic acid groups) • Acrylic monomer 1: ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER EG) • Acrylic monomer 2: Polyethylene glycol #600 dimethacrylate (n in general formula (1) is 14) (manufactured by NOF CORPORATION, PDE600) • Acrylic monomer 3: Polyethylene glycol #600 dimethacrylate (n of general formula (1) is 14) (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT ESTER 14EG) • Acrylic monomer 4: polyethylene glycol #1000 diacrylate (n of general formula (1) is 23) (manufactured by Shin-Nakamura Chemical Co, Ltd., A-1000)
（塑化劑） •塑化劑1：烯丙基樹脂（Kanto Chemical Co.,Inc.製，1,2-環己烷二羧酸雙（2-丙烯基）和丙烷-1,2-二醇的聚合物）(Plasticizer) •Plasticizer 1: Allyl resin (manufactured by Kanto Chemical Co., Inc., a polymer of 1,2-cyclohexanedicarboxylic acid bis(2-propenyl) and propane-1,2-diol)
（硬化促進劑） •咪唑硬化劑1：2-苯基-1H-咪唑-4,5-二甲醇（Shikoku Chemicals Corporation.製，2PHZ-PW）(Hardening accelerator) •Imidazole hardener 1: 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by Shikoku Chemicals Corporation, 2PHZ-PW)
（聚合起始劑） •自由基聚合起始劑1：二異丙苯基過氧化物（Kayaku Akzo Corporation製，Perkadox BC）(Polymerization initiator) • Radical polymerization initiator 1: Dicumyl peroxide (manufactured by Kayaku Akzo Corporation, Perkadox BC)
（含金屬之粒子） •銀粒子1：銀粉（Fukuda Metal Foil & Powder Co.,Ltd.製，HKD-38，片狀，D50 ：4μm） •銀塗層樹脂粒子1：鍍銀聚矽氧樹脂粒子（Mitsubishi Materials Corporation製，耐熱/表面處理10μm產品，球狀，D50 ：10μm，比重：2.3，銀的重量比率為50wt%，樹脂的重量比率為50wt%）(Metal-containing particles) •Silver particles 1: Silver powder (manufactured by Fukuda Metal Foil & Powder Co., Ltd., HKD-38, flake, D 50 : 4μm) •Silver coated resin particles 1: Silver-plated polysiloxane resin particles (Mitsubishi Materials Corporation, Ltd., heat / surface treatment products 10 m, spherical, D 50: 10μm, specific gravity: 2.3, the weight ratio of silver is 50wt%, the weight ratio of the resin of 50wt%)
（溶劑） •溶劑1：丁基丙三醇（BFTG）(Solvent) • Solvent 1: Butyl glycerol (BFTG)
＜導熱率λ的測量＞ 將得到之糊狀樹脂組成物塗佈於鐵氟龍板上，在氮氣環境下，花費60分鐘從30℃升溫至200℃，接著在200℃進行了120分鐘熱處理。藉此，得到厚度1mm的糊狀樹脂組成物的熱處理體（「鐵氟龍」為關於氟樹脂之註冊商標）。 接著，利用雷射閃光法，對熱處理體的厚度方向上的熱擴散係數α進行了測量。測量溫度為25℃。 又，利用示差掃描熱量（Differential scanning calorimetry：DSC）測量，對比熱Cp進行了測量。 進而，依據JIS K 6911對密度ρ進行了測量。 使用該等值，基於以下式，計算出導熱率λ。 導熱率λ[W/（m•K）]=α[m2 /sec]×Cp[J/kg•K]×ρ[g/cm3 ]<Measurement of thermal conductivity λ> The obtained paste-like resin composition was coated on a Teflon plate, heated from 30°C to 200°C in 60 minutes in a nitrogen atmosphere, and then heat-treated at 200°C for 120 minutes. Thereby, a heat-treated body of a paste resin composition with a thickness of 1 mm ("Teflon" is a registered trademark for fluororesin) was obtained. Next, using the laser flash method, the thermal diffusion coefficient α in the thickness direction of the heat-treated body was measured. The measurement temperature is 25°C. In addition, the differential scanning calorimetry (DSC) measurement was used to measure the contrast heat Cp. Furthermore, the density ρ was measured in accordance with JIS K 6911. Using these values, the thermal conductivity λ is calculated based on the following formula. Thermal conductivity λ[W/(m•K)]=α[m 2 /sec]×Cp[J/kg•K]×ρ[g/cm 3 ]
＜電阻率的測量＞ 將得到之糊狀樹脂組成物塗佈於玻璃板上，在氮氣環境下，花費60分鐘從30℃升溫至200℃，接著以200℃進行了120分鐘熱處理。藉此，得到厚度0.05mm的糊狀樹脂組成物的熱處理體。使用基於毫歐表（milliohm meter）（Hioki E.E. Corporation製）之直流四電極法、電極間隔為40mm的電極，對熱處理體表面的電阻值進行了測量。＜Measurement of resistivity＞ The obtained paste-like resin composition was coated on a glass plate, heated from 30°C to 200°C in 60 minutes in a nitrogen atmosphere, and then heat-treated at 200°C for 120 minutes. Thereby, a heat-treated body of a paste resin composition having a thickness of 0.05 mm was obtained. The resistance value of the surface of the heat-treated body was measured using a direct current four-electrode method based on a milliohm meter (manufactured by Hioki E.E. Corporation) with an electrode spacing of 40 mm.
＜25℃時的儲存彈性模數E’的測量＞ 將得到之糊狀樹脂組成物塗佈於鐵氟龍板上，花費60分鐘從30℃升溫至200℃，接著以200℃進行了120分鐘熱處理。藉此，得到厚度0.3mm的導熱性組成物的熱處理體。 從鐵氟龍板剝離得到之熱處理體，並將其設置於測量裝置（High-Tech Science Corporation.製、DMS6100）上，在拉伸模式、頻率1Hz的條件下進行了動態黏彈性測量（DMA）。藉此，對25℃時的儲存彈性模數E’（MPa）進行了測量。＜Measurement of storage elastic modulus E’ at 25℃＞ The obtained paste-like resin composition was coated on a Teflon plate, and the temperature was increased from 30°C to 200°C in 60 minutes, and then heat treatment was performed at 200°C for 120 minutes. Thereby, a heat-treated body of a thermally conductive composition having a thickness of 0.3 mm was obtained. The heat-treated body obtained by peeling off the Teflon sheet was set on a measuring device (manufactured by High-Tech Science Corporation, DMS6100), and the dynamic viscoelasticity measurement (DMA) was performed under the conditions of a tensile mode and a frequency of 1 Hz. . With this, the storage elastic modulus E'(MPa) at 25°C was measured.
＜斷裂強度的測量＞ 將得到之糊狀樹脂組成物塗佈於鐵氟龍板上，花費60分鐘從30℃升溫至200℃，接著以200℃進行了120分鐘熱處理。藉此，得到厚度0.3mm、寬度4mm的導熱性組成物的熱處理體。又，使用拉伸試驗機（Shimadzu Corporation製，「MST-1」）對各試驗樣品在25℃時的斷裂強度進行了測量。＜Measurement of breaking strength＞ The obtained paste-like resin composition was coated on a Teflon plate, and the temperature was increased from 30°C to 200°C in 60 minutes, and then heat treatment was performed at 200°C for 120 minutes. Thereby, a heat-treated body of a thermally conductive composition having a thickness of 0.3 mm and a width of 4 mm was obtained. In addition, a tensile tester (manufactured by Shimadzu Corporation, "MST-1") was used to measure the breaking strength of each test sample at 25°C.
＜斷裂應變的測量＞ 藉由將從伸長的原點（初始夾頭之間距離）到各試驗片的斷裂點（試驗片斷裂時的移位量）的伸長除以初始夾頭之間距離來計算出斷裂應變。＜Measurement of fracture strain＞ The breaking strain is calculated by dividing the elongation from the origin of the elongation (the distance between the initial chucks) to the breaking point of each test piece (the amount of displacement when the test piece breaks) by the distance between the initial chucks.
＜斷裂能量的測量＞ 藉由用移位對從伸長的原點（初始夾頭之間距離）到各試驗片的斷裂點（試驗片斷裂時的移位量）的應力進行積分來計算出斷裂點能量。將得到之斷裂點能量除以試驗片的體積，得到每單位體積的斷裂點能量（mJ/mm3 ）。<Measurement of breaking energy> The fracture is calculated by integrating the stress from the origin of elongation (distance between the initial chucks) to the breaking point of each test piece (the amount of displacement when the test piece breaks) by displacement. Some energy. Divide the obtained breaking point energy by the volume of the test piece to obtain the breaking point energy per unit volume (mJ/mm 3 ).
＜熱循環試驗/有無剝離之評價＞ 將糊狀樹脂組成物塗佈於表面鍍銀的基板上形成塗膜，在該塗膜上載置表面鍍金的7×7mm的矽晶片。其後，花費60分鐘從30℃升溫至200℃，接著以200℃進行了120分鐘熱處理。藉此，使導熱性組成物硬化，又，將矽晶片接合於基板。 用密封材料EME-G700ML-C（Sumitomo Bakelite Co.,Ltd.製）對接合後的矽晶片基板進行了密封。將其作為溫度循環試驗用樣品。 將樣品放入60℃/60%RH的高溫高濕槽中，處理48小時，其後，進行了260℃的回焊處理。 將回焊處理之後的樣品放入到溫度循環試驗機TSA-72ES（ESPEC CORP.製）中，以（i）150℃/10分鐘、（ii）25℃/10分鐘、（iii）-65℃/10分鐘、（iv）25℃/10分鐘為一次循環，進行了2000次循環處理。 其後，利用SAT（超音波探傷）確認了有無剝離。將未剝離者評價為○（良好），將剝離者評價為×（不良）。＜Thermal cycle test/Evaluation of the presence or absence of peeling＞ The paste-like resin composition is applied on a silver-plated substrate to form a coating film, and a 7×7 mm silicon wafer with a gold-plated surface is placed on the coating film. After that, it took 60 minutes to raise the temperature from 30°C to 200°C, and then heat treatment was performed at 200°C for 120 minutes. Thereby, the thermally conductive composition is hardened, and the silicon wafer is bonded to the substrate. The bonded silicon wafer substrate was sealed with a sealing material EME-G700ML-C (manufactured by Sumitomo Bakelite Co., Ltd.). Use this as a sample for temperature cycling test. The sample was placed in a 60°C/60%RH high-temperature and high-humidity bath for 48 hours, after which it was reflowed at 260°C. Put the sample after the reflow treatment into the temperature cycle tester TSA-72ES (manufactured by ESPEC CORP.), and set it to (i) 150°C/10 minutes, (ii) 25°C/10 minutes, (iii) -65°C /10 minutes, (iv) 25°C/10 minutes is one cycle, and 2000 cycles are performed. After that, SAT (ultrasonic flaw detection) was used to confirm whether there was peeling. Those who did not peel off were evaluated as ○ (good), and those who peeled off were evaluated as × (bad).
［表1］
由表-1的結果可知，藉由使用本發明的糊狀樹脂組成物接合半導體元件與基材，能夠得到長期表現出良好的導電性，長期可靠性優異的半導體裝置。From the results in Table-1, it can be seen that by using the paste resin composition of the present invention to bond a semiconductor element and a base material, a semiconductor device that exhibits good electrical conductivity over a long period of time and is excellent in long-term reliability can be obtained.
本申請主張基於2020年1月29日申請之日本特願2020-012506號之優先權，並將其揭示的全部內容援用於此。This application claims priority based on Japanese Patent Application No. 2020-012506 filed on January 29, 2020, and uses all the contents disclosed therein.
10:接著層 20:半導體元件 32（30）:晶片墊（基材） 34（30）:外引線（基材） 40:接合線 50:密封樹脂 52:焊球 100:半導體裝置10: Next layer 20: Semiconductor components 32 (30): Wafer pad (base material) 34 (30): Outer lead (base material) 40: Bonding wire 50: Sealing resin 52: Solder ball 100: Semiconductor device
[圖1]係示意性地表示半導體裝置的一例之剖面圖。 [圖2]係示意性地表示半導體裝置的一例之剖面圖。[FIG. 1] A cross-sectional view schematically showing an example of a semiconductor device. [FIG. 2] A cross-sectional view schematically showing an example of a semiconductor device.
10:接著層 10: Next layer
20:半導體元件 20: Semiconductor components
32(30):晶片墊(基材) 32(30): Wafer pad (base material)
34(30):外引線(基材) 34(30): Outer lead (base material)
40:接合線 40: Bonding wire
50:密封樹脂 50: Sealing resin
100:半導體裝置 100: Semiconductor device
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| JPH11150135A (en) * | 1997-11-17 | 1999-06-02 | Nec Corp | Conductive paste of superior thermal conductivity and electronic device |
| JP3428483B2 (en) * | 1998-02-17 | 2003-07-22 | 凸版印刷株式会社 | Pattern forming method, manufacturing method of plasma display rib substrate, manufacturing method of plasma display |
| JP2004139754A (en) | 2002-10-15 | 2004-05-13 | Mitsubishi Paper Mills Ltd | Silver oxide paste and manufacturing method of metal silver from silver oxide paste |
| JP2009295895A (en) * | 2008-06-09 | 2009-12-17 | Sumitomo Bakelite Co Ltd | Conductive paste for circuit board |
| JP2011122129A (en) | 2009-11-12 | 2011-06-23 | Sekisui Chem Co Ltd | Inorganic fine particle dispersed paste composition |
| JP5616070B2 (en) | 2010-01-21 | 2014-10-29 | 株式会社フジクラ | Electron beam curing conductive paste and circuit board manufacturing method using the same |
| JP2013026089A (en) | 2011-07-22 | 2013-02-04 | Fujikura Ltd | Conductive paste for electron beam hardening, and manufacturing method of circuit board using the same |
| JP2013067673A (en) * | 2011-09-20 | 2013-04-18 | Hitachi Chemical Co Ltd | Resin paste composition and semiconductor device |
| JP5567636B2 (en) * | 2012-10-05 | 2014-08-06 | 京セラケミカル株式会社 | Thermosetting resin composition for semiconductor bonding and semiconductor device |
| WO2016121806A1 (en) * | 2015-01-29 | 2016-08-04 | 住友ベークライト株式会社 | Paste adhesive composition, semiconductor device, method for manufacturing semiconductor device, and method for bonding heat radiation plate |
| JP6318137B2 (en) * | 2015-09-30 | 2018-04-25 | Ｄｏｗａエレクトロニクス株式会社 | Conductive paste and conductive film |
| JP2017130357A (en) * | 2016-01-20 | 2017-07-27 | 住友ベークライト株式会社 | Conductive paste and method for manufacturing cured body of conductive paste |
| JP2017130393A (en) * | 2016-01-21 | 2017-07-27 | 国立大学法人群馬大学 | Conductive paste and method for forming silver film |
| KR102040529B1 (en) * | 2016-08-19 | 2019-11-06 | 스미또모 베이크라이트 가부시키가이샤 | Die attach pastes and semiconductor devices |
| KR102029853B1 (en) * | 2016-10-31 | 2019-10-08 | 스미또모 베이크라이트 가부시키가이샤 | Thermally Conductive Pastes and Electronic Devices |
| JP7201296B2 (en) * | 2018-02-06 | 2023-01-10 | ローム株式会社 | Semiconductor device and its manufacturing method |
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